Three-component alkyl aluminum halide catalysts for olefin polym-erization



United States Patent "ice 3,230,208 THREE-CQMPQNENT ALKYL ALUMINUM HALIDE CATALYSTS FOR OLEFIN POLYM- ERIZATIGN Harry 1'. Coover, Jr., and Frederick E. Joyner, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Dec. 23, 1960, Ser. No. 77,339 The portion of the term of the patent subsequent to Sept. 15, 1981, has been disclaimed and dedicated to the Public Ciaims. (Cl. 260-93.7)

This application is a continuation-in-part of our copeuding application Serial No. 724,909, filed March 31, 1958, and now Patent No. 2,969,345.

This invention relates to a new and improved polymerization process and is particularly concerned with the use of a novel catalyst combination for preparing high molecular weight solid polyolefins, such as polypropylene, of high density and crystallinity. in a particular aspect the invention is concerned with the preparation of polypropylene and higher polyolefins using a particular catalyst combination which has unexpected catalytic activity,

and which gives products characterized by unusually high crystallinity, softening point, thermal stability, stiffness and being substantially free of non-crystalline polymers.

Polyethylene has heretofore been prepared by high pressure processes to give relatively flexible polymers having a rather high degree of chain branching and a density considerably lower than the theoretical density. Thus, pressures of the order of 500 atmospheres or more and usually of the order of 1000 to 1500 atmospheres are commonly employed. It has been found that more dense polyethylenes can be produced by certain catalyst combinations to give polymers which have very little chain branching and a high degree of crystallinity. The exact reason why certain catalyst combinations give these highly dense and highly crystalline polymers is not readily understood. Furthermore, the activity of the catalysts ordinarily depends upon certain specific catalyst combinations, and the results are ordinarily highly unpredictable, since relatively minor changes in the catalyst combination often lead to liquid polymers rather than the desired solid polymers.

Certain of the trialkyl aluminum compounds have been used in conjunction with inorganic halides to give high molecular weight polyethylene. Thus, triethyl aluminum in conjunction with titanium tetrachloride permits a low temperature, low pressure polymerization of ethylene to highly crystalline product. When this catalyst mixture is employed to polymerize propylene, the product is predominantly polymeric oils and rubbers with a comparatively small amount of high molecular weight crystalline products. Furthermore, a mixture of ethyl aluminum dihalide and titanium trihalide is ineffective as a polymerization catalyst, for example, for polymerizing propylene.

Some of the catalysts that are effective for producing crystalline high density polyethylene cannot be used to product a similar type of polypropylene. Thus, one cannot predict whether a specific catalyst combination will be effective to produce crystalline high density polymers with specific a-oleiins.

This invention is concerned with and has for an object the provision of improved processes whereby ot-monoolefins and particularly propylene can be readily polymerized by catalytic means to give high molecular weight, highly crystalline polymers. A particular object of the invention is to provide a catalyst combination which has unexpected catalytic activity for the polymerization of m-monoolefins to form crystalline high density polymers. Other objects will be apparent from the description and claims which 7 follow.

3,230,203 Patented Jan. 18, 1966 The above and other objects are attained by means of this invention, wherein ot-monoolefins, either singly or in admixture, are readily polymerized to high molecular weight solid polymers by effecting the polymerization in the presence of a catalytic mixture containing. an aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl and X is a halide selected from the group consisting of chlorine, bromine and iodine, a compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum, said compound being selected from the group consisting of halides, alkoxyhalides and acetylacetonates, and a third component selected from the compounds having the formulas: P(O)Y PY and YC(O) (cH2) C (O)Y wherein each Y is an alkylamino (-NR or alkoxy (-OR), said R being an alkyl radical containing 1 to 8, preferably 1 to 4, carbon atoms, and wherein n is an integer of 1 to 4. The catalytic activity of this mixture Was Wholly unexpected, particularly since the alkyl aluminum dihalides either singly or in admixture with the aforementioned etal compounds are ineffective as polymerization catalysts. Also, the third component of this catalyst composition is not an effective polymerization catalyst. The inventive process is carried out in liquid phase in an inert organic liquid and preferably an inert liquid hydrocarbon vehicle, but the process can be carried out in the absence of inert diluent. The process proceeds with excellent results over a temperature range of from 0 C. to 250 0, although it is preferred to operate Within the range of from about 50 C. to about 150 C. Likewise, the reaction pressures may be varied widely from about atmospheric pressure to very high pressures of the order of 20,000 psi. or higher A particular advantage of the invention is that pressures of the order of 30 to 1000 psi. give excellent results, and it is not necessary to employ the extremely high pressures which were necessary heretofore. The liquid vehicle employed is desirably one which serves both as a liquid reaction medium and as a solvent for the solid polymerization products at the temperature of polymerization.

The third component of the catalyst can be selected rom esters of carboxylic acids, lactones (intramolecular esters of carboxylic acids) and organic carbonates having the structural formulas:

(I? OR RCOOR (CH2)ru C O and C wherein R is selected from the group consisting of hydrogen, alkyl radicals containing 1 to 12 carbon atoms, phenyl, -(CH COOR wherein n is a number from 0 to 4, and

ooo1n 0 atoms. The polyethylene which is obtained in accordance with this invention has a softening or fusion point greater than C. whereby the products prepared therefrom can be readily employed in contact with boiling Water without deformation or other deleterious effects. The process of the invention readily results in solid polymers having molecular weights greater than 1000 and usually greater than 10,000. Furthermore, polymers having molecular weights of as much as 1,000,000 or higher can be readily prepared if desired. The high molecular weight, high density polyethylenes of this invention are insoluble in solvents at ordinary temperatures but they are soluble in such solvents as xylene, toluene or tetralin at temperatures above 100 C. These solubility characteristics make it possible to carry out the polymerization process under conditions wherein the polymer formed is soluble in the reaction medium during the polymerization and can be precipitated therefrom by lowering the temperature of the resulting mixture.

The polyethylenes of this invention are highly crystalline and usual-1y exhibit crystallinity above 80% as shown by X-ray diagrams. Ordinarily, the crystallinities of the polyethylenes obtained by this process average close to 90%. In contrast to the high pressure polyethylene known heretofore, the number of methyl groups per hundred carbon atoms in the polyethylenes of this invention are of the order of 0.5 or lower. The densities are of the order of 0.945 or higher, with densities of the order of 0.96 or higher being obtained in many cases. The inherent viscosity as measured in tetralin at 145 C. can be varied from about 0.5 or lower to 5 .0 or higher. Melt indices as measured by the standard ASTM method may be varied from about 0.1 to 100 or even higher.

The novel catalysts described above are particularly useful for polymerizing propylene to form a crystalline, highdensity polymer. The polypropylene produced has a softening point above 155 C. and a density of 0.91 and higher. Usually the density of the polypropylene is of the order of 0.91 to 0.92.

The polyoletfins prepared in accordance with the invention can be molded or extruded and can be used to form plates, sheets, films, or a variety of molded objects which exhibit a higher degree of stiffness than do the corresponding high pressure polyolefins. The products can be extruded in the form of pipe or tubing of excellent rigidity and can be injection molded into a great variety of articles. The polymers can also be cold drawn into ribbons, bands, fibers or filaments of high elasticity and rigidity. Fibers of high strength can be spun from the molten polyolefins obtained according to this process.

As has been indicated above, the improved results 0 tained in accordance with this invention depend upon the particular catalyst combination. Thus, one of the components of the catalyst is a compound of aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl. Among these hydrocarbon radicals are methyl, ethyl, propyl, butyl, phenyl, phenylethyl, naphthyl and the like, and the halogen selected from the group consisting of chlorine, bromine and iodine. The preferred alkyl aluminum dihalides are the lower alkyl derivatives, and the most preferred is ethyl aluminum dichloride. Another component of the catalyst composition is a compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum. In these compounds the transition metal can be at its maximum valence but it is possible to employ a compound of a transition metal having a reduced valence.- Among the transition metal compounds that can be used are the halides, alkoxyhalides and acetylacetonates of the above-named transition metals. Such compounds as titanium tetrachloride, titanium trichloride, dibutoxy titanium dichloride, diethoxy titanium dichloride and titanium acetylacetonate can be used in the catalyst combination. Similar compounds of zirconium, vanadium, chromium and molybdenum can also be used. For the most desirable results it is preferred to use a halide of titanium having either its maximum valency or a reduced valency and specifically it is preferred to employ either titanium tetrachloride or titanium trichloride in the catalyst composition. The third component of the catalyst composition is a carboxylic acid ester, or a lactone (an intramolecular ester of a carboxylic acid) or an organic carbonate.

Among the specific compounds that can be used are ethyl acetate, methyl carbonate, butyl propionate, benzyl acetate, cyclohexyl formate, 'y-valerolactone, butyl oxalate, methyl succinate, isopropyl phthalate, ethylene glycol diacetate, isob-utyl phenylacetate, sec-butyl formate, ethyl ncaproate, butyl benzoate, ethyl laurate, tetrahydrofurfuryl acetate, ethyl pelargonate, and the like.

The limiting factor in the temperature of the process appears to be the decomposition temperature of the catalyst. Ordinarily, temperatures from 50 C. to C. are employed, although temperatures as low as 0 C. or as high as 250 C. can be employed if desired. Usually, it is not desirable or economical to effect the polymerization at temperatures below 0 C. and the process can be readily controlled at room temperature or higher which is an advantage from the standpoint of commercial processing. The pressure employed is usually only suflicient to maintain the reaction mixture in liquid form during the polymerization, although higher pressures can be used if desired. The pressure is ordinarily achieved by pressuring the system with the monomer whereby additional monomer dissolves in the reaction vehicle as the polymerization progresses.

The polymerization embodying the invention can be carried out batchwise or in a continuous flowing stream process. The continuous processes are preferred for economic reasons, and particularly good results are obtained using continuous processes wherein a polymerization mixture of constant composition is continuously and progressively introduced into the polymerization zone and the mixture resulting from the polymerization is continuously and progressively withdrawn from the polymerization zone at an equivalent rate, whereby the relative concentration of the various components in the polymerization zone remains substantially unchanged during the process. This results in formation of polymers of extremely uniform molecular weight distribution over a rel atively narrow range. Such uniform polymers possess distinct advantages since they do not contain any substantial amount of the low molecular weight or high molecular weight formations which are ordinarily found in polymers prepared by batch reactions.

In the continuous flowing stream process, the temperature is desirably maintained at a substantially constant value within the preferred range in order to achieve the highest degree of uniformity. Since it is desirable to employ a solution of the monomer of relatively high con centration, the process is desirably effected under a pressure of from 30 to 1000 psi. obtained by pressuring the system with the monomer being polymerized. The amount of vehicle employed can be varied over rather wide limits with relation to the monomer and catalyst mixture. Best results are obtained using a concentration of catalyst of from about 0.1% to about 2% by weight based on the weight of the vehicle. The concentration of the monomer in the vehicle will vary rather widely depending upon the reaction conditions and will usually range from about 2 to 50% by weight. For a solution type of process it is preferred to use a concentration from about 2 to about 10% by weight based on the weigh of the vehicle, and for a slurry type of process higher concentrations, for example, up to 40% and higher are preferred. Higher concentrations of monomer ordinarily increase the rate of polymerization, but concentrations above 5 to 10% by weight in a solution process are ordinarily less desirable because the polymer dissolved in the reaction medium re sults in a very viscous solution.

The preferred molar ratio of aluminum compound to transition metal compound can be varied within the range .5 of 1:05 to 1:2, and the molar ratio of aluminum compound to the third component of the catalytic mixture can be varied within the range of 1:1 to 1:025, but it will be understood that higher and lower molar ratios are within the scope of this invention. A particularly effective catalyst contains one mole of transition metal compound and 0.5 mole of the third component per mole of aluminum dihalide. The polymerization time can be varied as desired and will usually be of the order of from 30 minutes to several hours in batch processes. Contact times of from 1 to 4 hours are commonly employed in autoclave type reactions. When a continuous process is employed, the contact time in the polymerization zone can also be regulated as desired, and in some cases it is not necessary to employ reaction or contact times much beyond one-half to one hour since a cyclic system can be employed by precipitation of the polymer and return of the vehicle and unused catalyst to the charging zone wherein the catalyst can be replenished and additional monomer introduced.

The organic vehicle employed can be an aliphatic alkane or cycloalkane such as pentane, hexane, heptane or cyclohexane, or a hydrogenated aromatic compound such as tetrahydronaphthalene or decahydronaphthalene, or a high molecular weight liquid paraffin or mixture of paratfins which are liquid at the reaction temperature, or an aromatic hydrocarbon such as benzene, toluene, xylene, or the like, or a halogenated aromatic compound such as chlorobenzene, chloronaphthalene, or othodichlorobenzene. The nature of the vehicle is subject to considerable variation, although the vehicle employed should be liquid under the conditions of reaction and relatively inert. The hydrocarbon liquids are desirably employed. Other solvents which can be used include ethyl benzene, isopropyl, benzene, ethyl toluene, n-propyl benzene, diethyl benzenes, mono and dialkyl naphthalenes, n-pentane, n-octane, iso octane, methyl cyclo hexane, tetralin, decalin, and any of the other well known inert liquid hydrocarbons. The diluents employed in practicing this invention can be advantageously purified prior to use in the polymerization reaction by contacting the diluent, for example, in a distillation procedure or otherwise, with the polymerization catalyst to remove undesirable trace impurities. Also, prior to such purification of the diluent the catalyst can be contacted advantageously with a polymerizable ozmonoolefin.

The polymerization ordinarily is accomplished by merely admixing the components of the polymerization mixture, and no additional heat is necessary unless it is desired to eifect the polymerization at an elevated temperature in order to increase solubility of polymer product in the vehicle. When the highly uniform polymers are desired employing the continuous process wherein the relative proportions of the various components are maintained substantially constant, the temperature is desirably controlled within a relatively narrow range. This is readily accomplished since the solvent vehicle forms a high percentage of the polymerization mixture and hence can be heated or cooled to maintain the temperature as desired.

The importance of the various components of this reaction mixture is evident from the fact that a mixture of ethyl aluminum dichloride and titanium trichloride is ineffective for polymerizing propylene. However, when the third component within the scope of this invention is added to the mixture the resulting catalyst composition is highly effective for polymerizing propylene to form a highly crystalline, high density, high softening polymer.

The invention is illustrated by the following examples of certain preferred embodiments thereof.

Example 1 Inside a nitrogen-filled dry box the following materials were placed into a dry 500 ml. pressure bottle: 100 ml. of dry heptane and 2 g. of catalyst mixture which comprised a 2:1:3 molar ratio respectively of ethylalurninum dichloride, ethyl acetate, and titanium trichloride. The pressure bottle was removed from the dry box and attached to a Parr hydrogenation apparatus in which propylene had been admitted to the reservoir in place of hydrogen. Shaking was initiated and the pressure bottle and its contents were heated to C. under 30 p.s.i. propylene pressure and maintained under these conditions for a total of 6 hours. The reaction mixture was detached from the shaking apparatus and dry methanol was added to destroy the catalyst. After several washes with hot, dry methanol a total of 11 g. of highly crystalline polypropylene was obtained from this reaction mixture. The inherent viscosity of the polypropylene was 3.8.

When a control run was carried out using ethylaluminum dichloride and titanium trichloride with no ethyl acetate present, a total of 2 g. of catalyst mixture gave no solid polypropylene under the above conditions.

Example 2 Inside a nitrogen-filled dry box, the following materials were placed into a 285 ml. stainless steel autoclave: 100 ml. of dried mineral spirits (B.P. 197 C.), a total of 1 g. of a 2:123 molar ratio of ethylalurninum dichloride, sec-butyl formate and titanium trichloride. This autoclave was then placed in a rocker attached to a source of dry liquid propylene and 100 ml. of dry propylene monomer was added. Rocking was initiated and the mixture was heated to C. and maintained there for a period of 4 hours. The polymer was worked up as described in Example 1, a yield of 39.0 g. being obtained having an inherent viscosity of 4.0.

When hydrogen was admitted to the polymerization zone and maintained there during the polymerization period at a pressure of 50 p.s.i., the inherent viscosity of the polypropylene obtained was 2.5. Upon increasing the hydrogen pressure to 500 p.s.i. the inherent viscosity of the polypropylene obtained was 0.40.

Example 3 The procedure of Example 2 was used to polymerize 1-butene using 1 g. of catalyst comprising a 221:2 molar ratio respectively of ethylalurninum dibromide, butyl pro ionate and titanium trichloride. A 38.5 g. yield of highly crystalline poly-l-butene was obtained.

Example 4 The procedure of Example 2 was employed to polymerize 3-methyl-l-butene using 1 g. of total catalyst com prising a 2:05 :3 molar ratio of ethylalurninum dichloride, ethyl laurate and vanadium trichloride. A 35.8 g. yield of highly crystalline poly(3-methyl-1-butene) was obtained.

Example 5 The procedure of Example 2 was employed to polymerize styrene using 1 g. of catalyst comprising a 121:3 molar ratio of ethylalurninum dibromide, ethyl pelargo nate and vanadium trichloride. A 24.0 g. yield of highly crystalline polystryrene was obtained.

Example 6 The procedure of Example 2 was employed to polymerize allylbenzene using 2 g. of catalyst comprising a 2: 1:3 molar ratio of cyclohexylaluminum dichloride, isobutyl phenyl acetate and zirconium tetrachloride. A good yield of highly crystalline poly(allylbenzene) was obtained.

Example 7 The procedure of Example 2 was employed to polymerize vinylcyclohexane using 1 g. of catalyst comprising a 1:1:1 molar ratio of phenylaluminum dichloride, methyl carbonate and molybdenum pentachloride. A 36.0 g. yield of highly crystalline poly(vinylcyclohexane) of inherent viscosity 2.7 was obtained.

Example 8 The procedure of Example 2 was employed to polymerize butadiene using 1 g. of catalyst comprising a 2:1:3 molar ratio of tolyl aluminum dichloride, benzyl acetate and titanium tetrabutoxide. A 20 g. yield of polybutadiene of inherent viscosity 1.8 was obtained.

Example 9 The procedure of Example 2 was followed except that the catalyst charge was 1 g. of a mixture of ethylaluminum dichloride, titanium trichloride and ethylene glycol diacetate in a molar ratio of 1:1:0.5. No solvent was employed and the polymerization temperature was 85 C. The crystalline polypropylene obtained had a density of 0.915 and an inherent viscosity of 2.85.

Other esters which may be used in place of ethylene glycol diacetate to give similar results include -valerolactone, butly oxalate, cyclohexyl formate, butyl benzoate, tetrahydrofurfuryl acetate and isopropyl phthalate.

Thus, by means of this invention polyolefins such as polyethylene and polypropylene are readily produced using a catalyst combination which, based on the knowledge of the art, would not be expected to be effective. The polymers thus obtained can be extruded, mechanically milled, cast or molded as desired. The polymers can be used as blending agents with the relatively more flexible high pressure polyethylenes to give any desired combination of properties. The polymers can also be blended with antioxidants, stabilizers, plasticizers, fillers, pigments, and the like, or mixed with other polymeric materials, waxes and the like. In general, aside from the relatively higher values for such properties as softening point, density, stiffness and the like, the polymers embodying this invention can be treated in similar manner to those obtained by other processes.

From the detailed disclosure of this invention it is quite apparent that in this polymerization procedure a novel catalyst not suggested in prior art polymerization procedures is employed. As a result of the use of this novel catalyst it is possible to produce polymeric hydrocarbons, particularly polypropylene, having properties not heretofore obtainable. For example, polypropylene prepared in the presence of catalyst combination within the scope of this invention is substantially free of rubbery and oily polymers and thus it is not necessary to subject such polypropylene of this invention to extraction procedures in order to obtain a commercial product. Also, polypropylene produced in accordance with this invention possesses unexpectedly high crystallinity, an unusually high softening point and outstanding thermal stability. Such polypropylene also has a very high stiffness as a result of the unexpectedly high crystallinity. The properties imparted to polypropylene prepared in accordance with this invention thus characterize and distinguish this polypropylene from polymers prepared by prior art polymerization procedures.

The novel catalysts defined above can be used to produce high molecular weight crystalline polymeric hydrocarbons. The molecular weight of the polymers can be varied over a wide range by introducing hydrogen to the polymerization reaction. Such hydrogen can be introduced separately or in admixture with the olefin monomer. The polymers produced in accordance with this invention can be separated from polymerization catalyst by suitable extraction procedures, for example, by washing with water or lower aliphatic alcohols such as methanol.

The catalyst compositions have been described above as being effective primarily for the polymerization of OC- monoolefins. These catalyst compositions can, however, be used for polymerizing other oc-OlCfiDS, and it is not necessary to limit the process of the invention to monoolefins. Other ot-olefins that can be used are butadiene, isoprene, 1,3-pentadiene and the like.

Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, variations and modifications can be effected within the spirit and scope of this invention as described hereinabove and as defined in the appended claims.

We claim:

1. In the polymerization of an olefinic hydrocarbon containing 3 to 10 carbon atoms to form solid, crystalline polymer, the improvement which comprises catalyzing the polymerization with a catalytic mixture containing an aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl and X is a halogen atom selected from the group consisting of chlorine, bromine and iodine, a halide of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum, and an ester having the formula RCOOR wherein R has the formula (CH COOR wherein n is a number from O to 4 and R and R are alkyl radicals containing 1 to 4 carbon atoms, the molar ratio of transition metal halide to said ester being within the range of 1:1 to 1:0.1.

2. In the polymerization of propylene to form solid, crystalline polymer, the improvement which comprises catalyzing the polymerization with a catalytic mixture containing an aluminum dihalide having the formula R AIX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl and X is a halogen atom selected from the group consisting of chlorine, bromine and iodine, a halide of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum, and an ester having the formula RCOOR wherein R has the formula (CH COOR wherein n is a number from O to 4 and R and R are alkyl radicals containing 1 to 4 carbon atoms, the molar ratio of transition metal halide to said ester being Within the range of1:1to1:0.1.

3. In the polymerization of propylene to form solid crystalline polymer the improvement which comprises effecting the polymerization in the presence of a catalytic mixture consisting essentially of ethyl aluminum dichloride and titanium trichloride and a molar ratio of titanium trichloride and ethylene glycol diacetate within the range of 1:1 to 1:0.1.

4. The method according to claim 3 wherein vanadium trichloride is used in the catalyst mixture in place of titanium trichloride.

5. The method according to claim 3 wherein ethyl aluminum dibromide is used in the catalyst mixture in place of ethyl aluminum dichloride.

6. As a composition of matter, a catalytic mixture consisting essentially of an aluminum dihalide having the formula R AlX wherein R is a hydrocarbon radical containing 1 to 12 carbon atoms and selected from the group consisting of alkyl, aryl and aralkyl and X is a halogen atom selected from the group consisting of chlorine, bromine and iodine, a halide of a transition metal selected from the group consisting of titanium, zirconium, vanadium, chromium and molybdenum, and an ester having the formula RCOOR wherein R has the formula -(CH ),,COOR wherein n is a number from O to 4 and R and R are alkyl radicals containing 1 to 4 carbon atoms, the molar ratio of transition metal halide to said ester being within the range of 1:1 to 110.1.

7. As a composition of matter, a catalytic mixture consisting essentially of a lower alkyl aluminum dihalide, a titanium halide and an ester having the formula RCOOR;

wherein R has the formula (CIfl MCOOR wherein n is a number from O to 4 and R and R are alkyl radicals 9 10 containing 1 to 4 carbon atoms, the molar ratio of titanium 2,954,367 9/1960 Vandenberg 26088.l halide to said ester being within the range of 1:1 to 1:0.1. 2 965 27 12 19 0 Field et 1 2 .94 9

8. As a composition of matter, a catalytic mixture of ethyl aluminum dichloride and titanium trichloride and 2996459 8/1961 Andersen et a1 252-429 a molar ratio of titanium trichloride and ethylene glycol 5 3088942 5/1963 coover et a1 26O 93'7 diacetate within the range of 1:1 to 1:0 1.

9. A composition according to claim 8 wherein va- FOREIGN PATENTS nadium trichloride is used in place of titanium trichloride. 559,727 1/ 1958 Belgium.

10. A composition according to claim 8 wherein ethyl 851,113 10/1960 Great Britain aluminum dibromide is used in place of ethyl aluminum 10 dichloride.

JOSEPH L. SCHOFER, Primary Examiner.

References Cited by the Examiner LESLIE H, GASTON, E i

UNITED STATES PATENTS 15 M. B. KURTZMAN, Assistant Examiner. 2,886,561 5/1959 Reynolds et al 260-93.7 

1. IN THE POLYMERIZATION OF AN OLEFINIC HYDROCARBON CONTAINING 3 TO 10 CARBON ATOMS TO FORM SOLID, CRYSTALLINE POLYMER, THE IMPROVEMENT WHICH COMPRISES CATALYZING THE POLYMERIZATION WITH A CATALYTIC MIXTURE CONTAINING AN ALUMINUM DIHALIDE HAVING THE FORMULA R1AIX2 WHEREIN R1 IS A HYDROCARBON RADICAL CONTAINING 1 TO 12 CARBON ATOMS AND SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND ARALKYL AND X IS A HALOGEN ATOM SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE AND IODINE, A HALIDE OF A TRANSITION METAL SELECTED FROM THE GROUP CONSISTING OF TITANIUM, ZIRCONIUM, VANADIUM, CHROMIUM AND MOLYBDENUM, AND AN ESTER HAVING THE FORMULA RCOOR1 WHEREIN R HAS THE FORMULA -(CH2)NCOOR2 WHEREIN N IS A NUMBER FROM 0 TO 4 AND R1 AND R2 ARE ALKYL RADICALS CONTAINING 1 TO 4 CARBON ATOMS, THE MOLAR RATIO OF TRANSITION METAL HALIDE TO SAID ESTER BEING WITHIN THE RANGE OF 1:1 TO 1:0.1. 